Manufacture of condensation products from olefines and naphthalene hydrocarbon compounds



Patented June 24, 1930 UNITED STATES PATENT OFFICE RICHARD MICHEL, F UERDINGEN, GERMANY, ASSIGNOR TO I. G. FARBENINDUSTRIE .AKTIENGESELLSCHAFT, OF FRANKIOBT-ON-THE-MAIN, GERMANY, A CORPORA- TION OF GERMANY MANUFACTURE OF CONDENSATION PIRDDUCTS FROM OL'EFINES AlN'D NAIPHTHALENE HYDROGABBON COMPOUNDS No Drawing. Application filed August 14, 1928, Serial No. 299,635, and in Germany August 22,1927.

' The invention relates to the manufacture of condensation products from naphthalene hydrocarbon compounds and. olefines and further relates to a process of separating ethylene from its higher homologues.

As I have set forth in my U. vS. Patent 1 No. 1,667,214 issued April 24th, 1928 homo that the homologues of ethylene react more readily than ethylene itself.

The present 'lIlVeDtlOIl represents a further development, and in accordance therewith I have found that the homologous olefines such as propylene, butylene and the like will react with naphthalene hydro- ,lene, homologous haphthal'enes e. g. ozor carbon compounds as for example naphthafi-methyl naphthalene, partially hydro- 5 genated naphthalenes, halogenated naphthalenes such as ozor o-chloro-naphthalene and the like, in the presence of catalytically acting substances at normal or even reduced.

pressure, whilst the temperature canbe reduced below the lower limits specified in my above-mentioned patent, even to roomtemperature and below. Under these milder conditions ethylene for all practical purposes 'does not enter in reaction while it is easy to unite the higher homologues quantitatively to the naphthalene nucleus. Thus, starting from gas mixtures containing ethylene, homologues thereof and possibly other gases,

that is for example oil gas, gaseous mixturesfrom oil cracking operations and the like,

40 the formation of valuable naphthalene derivatives is accompanied by a separation of the unsaturated constituents of the gas and a residual gas is obtained which can readily be worked up further to pure ethylene de rivatives as for example ethylene chlorhydrin, ethylene glycol and the like.-

Among the catalytically acting substances which have been found effective in uniting olefines with naphthalene hydrocarbon com'-' pounds are metallic halides particularly aluminium chloride andiron chloride, and addition compounds of, say, aluminium halides andolefines. With either of these catalysts there may be combined also, other substances capable of promoting the reac-- tion such as for example benzene hydrocarhens and halogen acids.

The resulting products are alkylated naphthalene hydrocarbon compounds and are found to consist predominantly or apparently exclusively of those having secondary alkyl residues. According to the relative proportions of the gas mixture and the naphthal'ene hydrocarbon compound used the final product contains as the principal constituent compounds with either one side chain or several side chains in respect to each molecule of the naphthalene hydrocarbon compound.

The followingexamples will illustrate my invention. The parts are by weight.

. Emample 1.

128 parts of naphthalene are melted and.

after adding 4 parts of anhydrous aluminium chloride a current of pure propylene is led in at C; with stirring. The propylens is completely absorbed. The reaction is interrupted when the increase in weight reaches 168 parts and after distillation of the crude product, from which the aluminiurn chloride is with advantage first removed in the known manner, for example by washing with water, a mixture of various propyl naphthalenes is obtained, which on cooling partly remain oily and partly solidify, to a crystalline mass. The crystals consist of a hydrocarbon of the probable composition 0 E1 which ay be regarded as tetra-isopropylnaphthalene. Analysisgives the following results Melting point: 26 C. 4

C found: 89.4% calculated: n 10.8% I Molecular weight 291 Example .2.

Propylene gas is introduced into a: mixture of 128 parts of melted naphthalene and '4 parts of anhydrous aluminium chloride at a temperature of from 110 to 120 C. and under a pressure of about 500mm. mercury. When an increase in weight of about 168 parts is attained, reaction-is interrupted and further treatment as shown in Example 1 yields the same products as those of Example 1.

Example 3. 128 parts by weight of naphthalene are condensed with propylene asdescribed in Example 1, but the reaction is interrupted when the increase inweight amounts to only 42 parts. The product remains liquid on cooling. After the addition of a further .one to two parts by weight oi aluminium chloride the product is treated with butvv lene (a mixture of 1:2- and 2: 3-butylene) at 20 C. with stirring. The butylene is completely absorbed and accordingto-the quantity introduced oils are obtained, containing an isopropyl group one or'several secondary butyl groups in the naphthalene nucleus.

Eeample .4.

v 1256 parts-of.-naphthalene and 5 parts of anhydrous aluminium chloride are heated to 80 =0. and treated with butylene -until' the mixture'forms a viscous paste at ordinary temperature. Then introducing butylene is continued whilst cooling the mixture to from '5Ito 10 C. until the total increase in weight amounts to 260 parts. Distillation in vacuo yields a principal fraction boiling from-200 to 250 .C. at'20 mm. pressure which .consists of buyl naphthalenes containing several side chains and being clear ,highly viscous oils; I

Eaiample 5;

i 128 parts of molten naphthalene are treated as describeddn Example 1 with an oil rent can be readilyregulated thus, that the gas, containing iroi'n about.15% to 25%o'f ethylene, from 8% to 15% of propylene and from 2% to 5% of 'butylene and higher homologues. The .velocity of the gas curescaping'gas contains only of olefines other than ethylene, while for all practical purposes the whole of'the ethylene present in the original gas is recovered.

of the corresponding secondary butyl naph thalenes. The escap ng ethylene containing gas can be further treated, for example with hypochlorous acid to form ethylene chlor-. hydrin or worked up to other, pure. ethylene derivatives, g g

Ewample 6.

To 250 parts by weight of tetrahydronaphthalene 12.5 parts by Weight of aluminium chloride are added. A current of propylene gas is led into this mixture at 20 to 30 C. with stirring until the wei ht has increased by about 140 parts. Disti ation yields an odorless transparent oil distilling at 150 to 200- C. under 20 mm. pressure.

. Example 7'. I

Propylene is led under normal atmo spheric pressure into 1200 parts of armonochlorotetrahydronaphthalene (obtamable by chlorinating tetrahydronaphthalene at a low temperature) and 50 parts of aluminium chloride whereupon the temperature rises to 90to 100 C., which is there maintained external application of heat.

The currentfof gas is interrupted as soon as the increase in weightamounts to 700' parts. Distillation in vacuo yields clear oils of amiddle viscosity consisting of propylated ar-chlorotetrahydronaphthalene.

In the following claims the generic'term .naphthalene hydrocarbon is used to denote naphthalene and its homologues and partially hydrogenated derivatives thereof eithersmgly or in admixture. Halogenated '-naphthalene hydrocarbons are considered to be equivalents of the aforesaid naphthalene hydrocarbons tion. 1

I claim: i 1. Process which comprises reacting with for carrying out this invenan olefine containing at least three carbon 1 atoms upon a naphthalene hydrocarbon in the presence of a catalytically active metallic halide under a pressure not essentially exceeding normal atmospheric pressure.

2. Process which comprises reacting with an olefine containing atleast threecarbon atoms upon a naphthalene hydrocarbon in the presence of a catalytically active metallic chloride under a pressure not essentially exceeding normal atmospheric pressure and at a temperature not exceeding 100 C.

- 3. Process which comprises reacting with an olefine containing at leastlthree carbon atoms upon a naphthalene hydrocarbon in. the presence of aluminium chloride undera pressure not essentially exceeding normal atmospheric pressure and at a temperature below 100 C. v

4. Process-which comprises .reacting with an olefi'nicgas containing a higher homo- 1 logue of ethylene upon a naphthalene hydrocarbonin the presence of a catalytically active metallic halide under a pressure not essentially exceeding normal atmospheric pressure and-at a temperature below 100. C.

5. Process which com rises reacting with an ol fi ic gas contaimnget ylene and, a

higher. homologue of ethylene upon a naphthalene hy ocarbon in the presence of a catalytically active metallic halide hinder a pressure not essentially exceeding normal naphthalene with a. gas having an olefine content of about 27% to 45%of which about to is ethylene and the remaining part consists of higher homologues of ethylene in the presence of a catalytically active my hand.

metallic halide under a pressure n'ot essentially exceedingnormal atmospheric ressure and at a temperature below 1.

In testimony whereof I have hereunto. set

RICHARD MICHEL;-

certificate 0F GORRECTiQN; Patent No. 1, 767,302.. I

RICHARD MICHEL,

It is hereby certified that error eppear s', in the printed specificationof the -.above m b rr patent requiringeorrection as-tollows: Page I; strike out line 21, and insert the same to follow line 22, the lines having been transposed; and -that' the said Letters Patent should be read with this correctiontherein that the saine may ieonformtothe record of thejcase jnthe Patent 0ffjce.-

' Signed'an'd sealed this emery of September, A. D. 1930.

T .-Aeting Commissioner 0t Patents.

Gra ntedJun'e 1930, m; 

